Determination of total iron in standard rocks by spectrophotometric titration with EDTA

A method for the determination of total iron in silicate rocks is described. It is based on spectrophotometric titration of iron(III) with EDTA after decomposition in a PTFE bomb. No prior separation of interfering elements is needed. The method was tested by analysis of the U.S. Geological Survey reference rocks G-2, AGV-1, GSP-1, BCR-1 and PCC-1. The same sample solutions were also analysed by atomic-absorption spectrophotometry. The agreement with published and recommended values was good.     

A selective lon-exchange separation and spectrophotometric determination of traces of copper in silicate rocks

Summary A combined cation-exchange separation-spectrophotometric procedure has been worked out for the accurate determination of traces of copper in silicate rocks. Silicates are opened up with sulfuric and hydrofluoric acids. The residue is taken up into a 0.5 M hydrochloric acid −0.05 M oxalic acid −1% hydrogen peroxide solution and loaded on a strongly acidic cation-exchange resin column. Polyvalent ions including ferric ions do not adsorb on the column, while copper (II) retains together with divalent metal ions as well as aluminum (III). Copper (II) can selectively be eluted by a small volume of 0.05 M thiosulfate solution. This fraction is sufficiently pure to allow a direct spectrophotometric determination of copper with Na-DDTC without the addition of tartrate and EDTA as masking agents. Quantitative results are quoted for the determination of copper in international standard rocks of the Geological Survey of Japan (GSJ) and the U.S. Geological Survey (USGS).     

Anion-exchange separation and spectrophotometric determination of molybdenum and tungsten in silicate rocks

A combined ion-exchange spectrophotometric method has been developed for the determination of molybdenum and tungsten in silicate rocks. After the decomposition of samples with a mixture of sulphuric, nitric and hydrofluoric acids, traces of molybdenum and tungsten are separated from other elements by anion-exchange in acid sulphate media containing hydrogen peroxide. The adsorbed molybdenum and tungsten can easily be stripped from the column by elution with sodium hydroxide-sodium chloride solution. The adsorption and desorption steps provide selective concentration of molybdenum and tungsten, allowing the simultaneous spectrophotometric determination of the two metals with dithiol. Results on the quantitative determination of molybdenum and tungsten in the U.S. Geological Survey standard samples are included.     

Ultraviolet spectrophotometric determination of copper in copper ores by flow-injection analysis

A flow-injection analysis (FIA) method for the ultraviolet spectrophotometric determination of copper in copper ores is described. The ore samples are dissolved in concentrated perchloric acid, the excess acid is neutralized with ammonia solution, and the resulting solution is used for the determination of copper. The UV-FIA system is based on the reaction of copper (II) ions with pyrophosphate and subsequent measurement of the absorbance of the dipyrophosphatocuprate (II) complex at 240 nm. The main factors which control the formation of this complex and the FIA variables influencing the system are discussed. The calibration graph is linear from 2-50 ppm copper. At a sampling rate of about 70 samples h(-1) with 50 mul sample injections, precision was about 1% relative standard deviation. Results obtained compare well with those obtained by atomic absorption spectrometry.     

Flow-injection analysis of silicate rocks for total iron and aluminium

A flow-injection method is described for the spectrophotometric determination of total iron and aluminium in silicate rocks. Rock samples are opened up by fusion with a mixture of lithium carbonate and boric acid, the melt is taken up in 1M hydrochloric acid and the resulting solution is used for the determination of both iron and aluminium. The flow system for the determination of iron needs no particular reagents, involving simply measurement of the absorbance of the chloro-complex of iron(III) at 335 nm. The system for aluminium consists of the reduction of iron(III) to iron(II), colour development with Xylenol Orange (XO), destruction of XO-chelates other than that of aluminium by addition of EDTA and subsequent measurement of the absorbance of the aluminium-XO complex at 506 nm. The systems permit semi-automatic, rapid analysis of silicate rocks for iron and aluminium. Results obtained for standard rocks were in good agreement with the recommended values. The precision ranged from 0.1 to 0.9% for iron and from 0.3 to 0.7% for aluminium.     

Fluorimetric differential-kinetic determination of silicate and phosphate in waters by flow-injection analysis

A flow-injection analysis (FIA) method for simultaneous determination of silicate and phosphate, based on the different rates of formation of their molybdate heteropoly acids is suggested. The fluorimetrically monitored product is thiochrome, formed by oxidation of thiamine by the heteropoly acid. The FIA configurations designed allow performance of two measurements at different times on each sample injected. The method permits the determination of these anions in the range 30-600 ng ml in ratios from 1:10 to 10:1 and can be applied to samples of running and bottled water with good results. The sampling frequency achievable is 60 hr .     

Sequential determination of iron and titanium by flow-injection analysis

A flow-injection method has been developed for the sequential spectrophotometric determination of iron and titanium using 3,4 dihydroxybenzoic acid as chromogenic reagent. The system involves the sequential measurement of the absorbances of the complexes at 380 and 570 nm. The system is designed using a simultaneous injection of sample and reagent into separate carrier streams. The proposed method is characterized by a precision of about 2%, a sampling rate of about 50 samples per hour, and a reagent consumption of 200 mul (0.50% solution) per sample. It is relatively free of interferences and was used for the sequential determination of titanium and iron in rocks.     

Rapid determination of nanogram amounts of tellurium in silicate rocks

A hydride-generation flameless atomic-absorption technique is used to determine as little as 5 ng g^-1 tellurium in 0.25 g of silicate rock. After acid decomposition of the sample, tellurium hydride is generated with sodium borohydride and the vapor passed directly to a resistance-heated quartz cell mounted in an atomic-absorption spectrophotometer. Analyses of 11 U.S. Geological Survey standard rocks are presented.     

Sensitivity improvement of ammonia determination based on flow-injection indophenol spectrophotometry with manganese(II) ion as a catalyst and analysis of exhaust gas of thermal power plant.

The sensitivity improvement of a flow-injection spectrophotometric method for the determination of ammonia was examined based on an indophenol blue coloration reaction with salicylate and hypochlorite in the presence of manganese(II) as a reaction promotion catalyst. The optimal conditions for achieving higher sensitivity of ammonia determination were examined using a three-line flow system. The limit of detection corresponding to a signal-to-noise ratio (S/N) of 3 was 0.005 mg l(-1) (approximately equal to 5 ppb) of NH4+. A calibration graph was linear in the range from 5 ppb to 1,000 ppb of ammonium ion. The relative standard deviations (n = 9) for 50 ppb and 100 ppb of ammonium ion were 6.4% and 2.2%, respectively. The proposed method was applied to the determination of ammonia in the exhaust gas of a thermal power plant. Prior to the FIA determination, ammonia in the exhaust gas was absorbed into a boric acid solution; the absorption solution was then analyzed by the proposed FIA.     

Simultaneous determination of iron(III) and vanadium(V) by use of a kinetic-spectrophotometric and rapid mixing flow system

The quantitative spectrophotometric determination of V(V) by its catalytic effect on the oxidation of chromotropic acid [the disodium salt of 4,5-dihydroxynaphthalene-2,7-disulphonic acid (CS)] by potassium bromate has been adapted to a flow system employing a rapid sample and reagent introduction manifold, in which valves and carrier streams are omitted without decreasing the precision or increasing the sample consumption relative to flow-injection analysis (FIA). Measurements are made at 420 nm. Coexisting Fe(III) can be determined simultaneously at the same wavelength by its more rapid colour chelate formation with CS. An accurate determination of V(V) and Fe(III) in the mixture was developed with a sample throughput of about 60 hr.     

Flow-injection systems for determination of trace manganese in various salts by catalytic photometric detection

Two flow-injection analysis (FIA) systems for the determination of trace manganese in salts are presented using highly sensitive catalytic detection based on the oxidation of 3,4-dihydroxybenzoic acid by hydrogen peroxide. Two different approaches, the use of a large sample volume injection in a usual FIA mode (system A) and on-line coupling of a cation-exchange separation column with detection in a continuous flow system (system B), have proved very effective for eliminating the blank peak problem and thus affording direct injection of a sample solution containing a large concentration of salt. The limits of determinations are 0.04 ppm and 0.01 ppm for systems A and B respectively, when a 5 g sample is used for preparing the 100 ml sample solution. The proposed FIA systems were satisfactorily applied to the determination of manganese at 0.03-1.59 ppm in solar salts (salts made by exposing brine to the sun) with good precision.     

Determination of ortho- and pyrophosphates in waters by extraction chromatography and flow-injection analysis

Extraction-chromatographic separation of ortho- and pyrophosphate anions on an inert support modified with an organotin extractant was studied and used for their subsequent determination in a flow-injection system. The proposed FIA manifold includes an extraction-chromatographic mini-column, on which the phosphate anions are separated and preconcentrated, and a post-column spectrophotometric detector. For the determination of orthophosphate, the absorbance of the reduced 12-molybdophosphoric acid is monitored at 660 nm. The sum of ortho- and pyrophosphate can be determined after preliminary hydrolysis of pyrophosphate to orthophosphate in neutral solution at 50 degrees by use of inorganic pyrophosphatase. For a sample volume of 6 ml, the calibration graph is linear within a range of 5.0-100.0 ng/ml P. The limit of detection is 0.3 ng/ml P. The recovery of the ions to be determined is not less than 96%, the relative error is not worse than 4%. The proposed method was used for the analysis of river water samples.     

Determination of cobalt in zinc electrolyte by an automated flow-injection system

A flow-injection method has been developed for the spectrophotometric determination of cobalt in zinc electrolyte using 2-(5-bromo-2-pyridylazo)-5-(N-propyl-N-sulphopropylamino)aniline (5-Br-PSAA) as chromogenic reagent. A sample solution is injected into a carrier containing hydrochloric acid, diammonium hydrogenphosphate and hydrogen peroxide. The sample is then merged with the stream of ammonium acetate solution and PSAA solution is synclonously injected into the sample zone. After mixing with 2M sulphuric acid, the absorbance of cobalt-PSAA complex is measured at 617 nm. The flow injection system proposed is fully controlled with a personal computer. The flow-injection system permits throughput of 12 samples per hour. The relative standard deviation (n = 10) for 0.1 mug Co/ml solution is 5.0%.     

Spectrophotometric determination of silicate with Rhodamine B by flow-injection analysis

A spectrophotometric flow-injection method for the determination of silicate based on the formation of an ion pair between molybdosilicic acid and Rhodamine B is proposed. It allows silicate to be determined over the concentration range 0.17–2.0 mg 1^?1 at a sampling rate of 40 h^?1, is reasonably precise and is highly tolerant to ions that commonly occur in waters. It has been applied with satisfactory results to the determination of silicate in various types of water.     

New scheme for complete silicate analysis based on ion-exchange chromatography

Summary A new method has been developed for the quantitative separation and determination of Si, Ti, Al, total iron, Mn, Mg, Ca, Na, K and P in silicate rock samples. Silicate is decomposed by fusion with a mixture of boric acid and lithium carbonate and the melt is dissolved in 1 M hydrochloric acid. The diluted sample solution is loaded on a column of AG 50W, X-8 sulfonated polystyrene cation-exchange resin and the elements Fe, Mn, Ti, Al-Mg and Ca are eluted by stepwise changing eluting agents. Si and P are eluted together without retention and are spectrophotometrically determined in the effluent without any separation. The Al-Mg mixture is further separated by simple anion exchange in the same eluent system as used in the preceding cation-exchange chromatography. Na and K are accurately determined in an aliquot of the original sample solution without any separation by flame atomic absorption spectrometry. Recoveries of 10 major and minor elements are satisfactory. Results are quoted of the quantitative analyses of four standard rocks of the U. S. Geological Survey and Geological Survey of Japan.

---

Neues Schema zur quantitativen Gesamtanalyse von Silicaten durch Ionenaustausch-Chromatographie

Zusammenfassung Eine neue Methode wurde entwickelt zur quantitativen Trennung und Bestimmung von Si, Ti, Al, Gesamt-Fe, Mn, Mg, Ca, Na, K und P in Proben von Silicatgestein. Hierbei wird das Silicat durch Schmelzen mit einer Mischung von Borsäure und Lithiumcarbonat aufgeschlossen und die Schmelze in 1 M Salzsäure gelöst. Die verdünnte Lösung wird auf eine Kationenaustauschersäule (AG 50W, X-8, sulfoniertes Polystyrol) gegeben und die Elemente Fe, Mn, Ti, Al-Mg und Ca werden mit Hilfe von stufenweise variierten Elutionsmitteln eluiert. Si und P werden gemeinsam ohne Retention eluiert und ohne Trennung spektralphotometrisch im Eluat bestimmt. Al und Mg werden durch Anionenaustausch mit demselben Elutionssystem wie in der vorangegangenen Kationenaustausch-Chromatographie getrennt. Na und K können zuverlässig aus der ursprünglichen Lösung ohne Trennung mittels Flammen-AAS bestimmt werden. Die Wiederfindung für 10 Hauptund Nebenbestandteile ist zufriedenstellend. Das Verfahren wurde zur Analyse von vier Standardgesteinen des US Geological Survey und des Geological Survey of Japan angewendet.

---

---

This work was in part supported by a Grant-in-Aid for Scientific Research (No. 60540364) from the Ministry of Education, Science, and Culture.     

Determination of rare-earth elements and yttrium in silicate rocks by sequential inductively-coupled plasma emission spectrometry

An ICP—AES method for determination of rare-earth elements (REE) and yttrium at trace levels in silicate rocks is described. The method involves decomposition of the rock sample by heating with a mixture of hydrofluoric and perchloric acid, followed by precipitation of the REE and Y as oxalates, with calcium as carrier. The oxalate precipitate is ignited to the oxide, which is then dissolved in dilute nitric acid and the solution is used for ICP—AES measurements, with use of pure REE solutions as calibration standards. The method has been applied to the determination of REE in a number of standard reference materials and the results have been compared with the reported values. Three other silicate rock samples have also been analysed for REE and Y by this method.     

Determination of aluminum in beverages by automated non-segmented continuous flow analysis with fluorescent detection of the lumogallion complex

A method for the automated determination of aluminum in a variety of beverages is described. The method utilizes lumogallion as a complexing agent in a buffer solution. The system is very similar to flow-injection analysis (FIA), however, the tubing id is larger than that typically used in FIA. Therefore, the system is best described as non-segmented continuous flow analysis using fluorescence spectroscopy detection. The method is extremely simple, requiring virtually no sample preparation and only one reagent. The instrument detection limit for aluminum is 0.012 microgram ml-1 and calibration is linear to 3 micrograms ml-1. Results from a variety of beverage matrices are discussed and compared with the frequently used 8-hydroxyquinolone method utilizing a chloroform extraction and fluorescence spectroscopy detection.     

Determination of trace quantities of scandium in silicate rocks by a combined ion exchange-spectrophotometric method

A spectrophotometric determination of scandium in silicate rocks has been developed with arsenazo as the color reagent. After the decomposition of samples with a hydrofluoric-perchloric acid mixture, traces of scandium are separated from interferences by cation- and anion-exchange in acid sulfate media and anion exchange in hydrochloric acid solution. The successive 3 steps, with an intermediate concentration step, yield scandium in a sufficiently pure state for spectrophotometric determination.     

Development of a spectrophotometric determination of siderophores using flow-injection analysis

A method has been developed for the spectrophotometric determination of siderophores using flow-injection analysis (FIA) based on the reaction of siderophores with the ternary complex Eriochrome Cyanine R-Fe(III)-cetyltrimethylammonium bromide. 2,3-Dihydroxybenzoic acid, 2,3-dihydroxynaphthalene, and tolypocine were used as the model iron-binding ligands. The calibration curve for one of the siderophores (tolypocine) is linear in the concentration range 2.6 x 10(-6)-1.5 x 10(-4)M. The determination limit (10sigma) for tolypocine was 2.6 x 10(-6)M. The applicability of the method was demonstrated on the determination of the complexation ability of siderophores produced by some entomopathogenic fungi. Samples can be analysed at a rate of 30 samples per hour.     

Determination of palladium, platinum and rhodium in geologic materials by fire assay and emission spectrography

A method is described for the determination of palladium down to 4ppb (parts per billion, 10(9)), platinum down to 10 ppb and rhodium down to 5 ppb in 15 g of sample. Fire-assay techniques are used to preconcentrate the platinum metals into a gold bead, then the bead is dissolved in aqua regia and diluted to volume with 1M hydrochloric acid. The solution is analysed by optical emission spectrography of the residue from 200 mul of it evaporated on a pair of flat-top graphite electrodes. This method requires much less sample handling than most published methods for these elements. Data are presented for G-1, W-1, and six new standard rocks of the U.S. Geological Survey. The values for palladium in W-1 are in reasonable agreement with previously published data.